Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Treating polymer containing material or treating a solid...
Reexamination Certificate
1999-12-20
2001-04-03
Boykin, Terressa M. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Treating polymer containing material or treating a solid...
Reexamination Certificate
active
06211332
ABSTRACT:
The present invention relates to a process for reducing the molecular weight of copolymers and terpolymers of ethylene having an ethylene content not exceeding 20%, particularly ethylene-propylene (EPM) or ethylene-propylenediene (EPDM) elastomers.
The molecular weight reduction of EP(D)M by means of an operation downstream of the polymerization is a very advantageous technology for the preparation of polymers having low molecular weights and therefore low viscosities.
When evaluating the advantages of effecting the degradation of standard polymers to obtain polymers with the desired molecular weight, the difficulty of producing a high fluidity and consequently sticky polymer without any form stability, in an industrial plant, should be taken into account. The greater the elastomeric nature of the material, the more evident this becomes.
Various techniques are known in literature which allow depolymerization, i.e. the reduction of the molecular weight. In particular, thermo-oxidation, thermodegradation and degradation by means of radical initiators (peroxides), are used.
Thermo-oxidation (see for example U.S. Pat. No. 4,372,863) is a process carried out in the presence of oxygen (or air), which causes degradation by the combination of mechanical shear, temperature and the effect of oxygen. The known techniques mainly relate to the use of equipment in batch, long treatment times and machines only partially filled to guarantee a sufficient air flow. The resulting material is dark, oxidated and difficult to handle.
Thermo-mechanical degradation (see CA-A-991,792) is carried out at a very high temperature (about 330-400° C.), under nitrogen and preferably in extrusion; when operating under these thermal conditions, the radicals formed by mechanical shear and thermal stress do not have a sufficient life time to recombine.
The degradation reaction with peroxides is known and widely used in the field of polyalpha-olefins containing less than 20% approximately of ethylene (see for example CA-A-999,698). This is due to the instability of the radical on the tertiary carbon which prevents it from undergoing further cross-linking reactions which, on the contrary, are characteristic of EP(D)M and which are the basis of peroxide vulcanization reactions.
EP-A-123,424 describes a method for the degradation of olefinic polymers in the presence of a mixture essentially consisting of a peroxide and a hydroperoxide.
A process has now been found which allows an extremely strong acceleration in the degradation of the polymeric material, even at temperatures not exceeding 200° C., to be obtained.
In accordance with this, the present invention relates to a process for the reduction of the molecular weight of a polymeric material selected from EPM copolymer and EPDM terpolymer and relative mixtures, which comprises treatment of the polymeric material with at least one hydroperoxide, the above hydroperoxide being present in such a quantity as to cause a reduction in the molecular weight.
With respect to the EPM copolymers which can be used in the process of the present invention, these ethylene/propylene copolymers have a propylene molar content ranging from 16% to 50%, preferably from 20% to 45%, and an Mn ranging from 10,000 to 200,000.
With respect to EPDM, these are non-conjugated ethylene/propylene/diolefin terpolymers. Typical examples of non-conjugated diolefins are 1,4-hexadiene, 1,5-heptadiene, 1,6-octadiene, 1,4-cyclohexadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene. These EPDM terpolymers usually have an ethylene molar content ranging from 30 to 85%, preferably from 40 to 70%; from 15 to 70%, preferably from 30 to 60% molar, of propylene; from 0.5 to 20% molar, preferably from 1 to 15%, even more preferably from 2 to 10% molar of non-conjugated diene. The molecular weights Mn of EPDM are within the range of 15,000 to 200,000, preferably from 20,000 to 70,000 and the non-conjugated diene is preferably 5-ethylidene-2-norbornene.
The process for the preparation of EPDM in the presence of Ziegler-Natta catalysts is well known; see for example U.S. Pat. No. 2,933,589; U.S. Pat. No. 3,000,866; U.S. Pat. No. 3,093,621. These terpolymers are mainly produced as components for elastomeric compositions and are characterized by the absence of unsaturation in the main chain and by the presence of unsaturation sites in cyclic groups or groups lateral to the main chain.
In the process of the present invention, mixtures of polymers can also be used. Useful mixtures are mixtures of two or more EPM having a different ethylene content and/or different molecular weight.
The temperature at which the process of the present invention takes place ranges from 80° C. to 250° C., preferably from 140° C. to 200° C.
As far as the hydroperoxide (or mixture of hydroperoxides) is concerned, this is added to the EP(D)M as such or dissolved in a suitable solvent, preferably dissolved in a suitable solvent. The hydroperoxide should preferably have the characteristic of not undergoing significant decomposition at the process temperature. In other words, it is preferable for the hydroperoxide to have a half time which should not be less than the process time, even more preferably not less than 10 times the process time.
Typical examples of hydroperoxides are cumene hydroperoxide, hydrogen peroxide, t-butyl hydroperoxide, 2,5-dihydroperoxy-2,5-dimethylhexane. The concentration of hydroperoxide with respect to the EP(D)M ranges from 0.1 to 20% by weight, preferably from 0.2 to 10% by weight, even more preferably from 0.5% to 5% by weight.
In a preferred embodiment, the process of the present invention is carried out under high shear conditions, usually higher than 100 sec
−1
, preferably higher than 1000 sec
−1
.
The process of the present invention is preferably carried out in an extruder, even more preferably in a twinscrew extruder.
The process of the present invention is carried out without the introduction of oxygen and can be effected both in batch and in continuous. In the batch operation, the single components are added in a suitable reactor together or portion wise, in the presence of or without a solvent, preferably without a solvent. When operating in continuous, the reagents are added continuously, at a suitable feeding rate, to a reactor (or reactor zone) thermostat-regulated at the desired temperature.
The products which can be obtained with the process of the present invention can be applied in many fields, particularly in those which necessitate low molecular weights. Typical applications of these products are as viscosity modifiers in the engine oil-lubricant field, the modification of high fluidity plastic materials.
The following examples are provided for a better understanding of the present invention.
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Boykin Terressa M.
Enichem S.p.A.
Oblon & Spivak, McClelland, Maier & Neustadt P.C.
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